Vibrational spectroscopy and DFT calculations of N,N′‐dicyclohexylcarbodiimide

Infrared (IR) and Raman spectra were obtained for N,N′‐dicyclohexylcarbodiimide (DCC) in the solid state and in CHCl₃ solution. Structures and vibrational spectra of isolated, gas‐phase DCC molecules with C₂ and C_i symmetries, computed at the B3‐LYP/cc‐pVTZ level, show that the IR and Raman spectra provide convincing evidence for a C₂ structure in both the solid state and in CHCl₃ solution. Using a scaled quantum‐chemical force field, these density functional theory calculations have provided detailed assignments of the observed IR and Raman bands in terms of potential energy distributions. Comparison of solid‐state and solution spectra, together with a Raman study of the melting behaviour of DCC, revealed that no solid‐state effects were evident in the spectra. Copyright © 2010 John Wiley & Sons, Ltd.     

Adsorption of 2‐amino‐5‐cyanopyridine on a gold surface as probed by surface‐enhanced Raman spectroscopy

The adsorption of 2‐amino‐5‐cyanopyridine (2‐ACP) was investigated in solution at different pH values by i n situ surface‐enhanced Raman scattering (SERS) spectroscopy combined with the electrochemical method. The assignments of the main bands were first performed on the basis of the spectral features of similar compounds and with the help of density functional theory calculations. The results revealed that the adsorption and the interfacial structure of 2‐ACP on the Au electrode depended on the applied potential and the pH values of the solution. In the natural solution, 2‐ACP was adsorbed on the surface with a vertical orientation by the CN group from − 0.4 to − 1.0 V, whereas in the − 0.4 to 0.8 V range, the N atom of the pyridine ring was bound to the surface. A transition region for the reorientation of the two adsorption modes was observed from − 0.8 to − 0.4 V. A flat configuration was preferred at an extremely negative potential. A similar surface adsorption behavior was observed in the alkali environment, while the Stark effect slope decreased because of the adsorption of OH⁻. Due to the protonation of N atom in the acidic solution, the potential region for the coexistence of two configurations ranged from − 0.4 to 0.2 V. Additionally, a similar adsorption configuration was proposed on the Au colloids at various pH values. The results revealed that the adsorption behavior became more complex on colloidal surfaces than that on a rigid electrode surface. Copyright © 2010 John Wiley & Sons, Ltd.     

Absorption and resonance Raman spectroscopy of the 1Bu state of trans‐1,3,5‐hexatriene including vibronic coupling

The vibronic coupling between the first excited S₁ (2¹A_g) and the second excited S₂ (1¹B_u) singlet electronic states in spectroscopy of trans‐1,3,5‐hexatriene molecule is investigated on the basis of a model consisting of two electronic states coupled by two vibrational modes. Employing a perturbation theory that treats the intramolecular couplings in a perturbative manner, the absorption and resonance Raman cross sections and excitation profiles of this molecule are calculated using the time‐correlation function formalism. The non‐Condon corrections are included in evaluation of cross sections. The multidimensional time‐domain integrals that arise in these calculations have been evaluated for the case in which S₀ (1¹A_g) S₂ (1¹B_u) electronic transition takes place between displaced and distorted harmonic potential energy surfaces. The calculated spectra are in good agreement with the experimental ones. Copyright © 2011 John Wiley & Sons, Ltd.     

A Raman spectroscopic study of the different vanadate groups in solid‐state compounds—model case: mineral phases vésigniéite [BaCu3(VO4)2(OH)2] and volborthite [Cu3V2O7(OH)2·2H2O]

Raman spectroscopy has been used to study vanadates in the solid state. The molecular structure of the vanadate minerals vésigniéite [BaCu₃(VO₄)₂(OH)₂] and volborthite [Cu₃V₂O₇(OH)₂·2H₂O] have been studied by Raman spectroscopy and infrared spectroscopy. The spectra are related to the structure of the two minerals. The Raman spectrum of vésigniéite is characterized by two intense bands at 821 and 856 cm⁻¹ assigned to ν₁ (VO₄)³⁻ symmetric stretching modes. A series of infrared bands at 755, 787 and 899 cm⁻¹ are assigned to the ν₃ (VO₄)³⁻ antisymmetric stretching vibrational mode. Raman bands at 307 and 332 cm⁻¹ and at 466 and 511 cm⁻¹ are assigned to the ν₂ and ν₄ (VO₄)³⁻ bending modes. The Raman spectrum of volborthite is characterized by the strong band at 888 cm⁻¹, assigned to the ν₁ (VO₃) symmetric stretching vibrations. Raman bands at 858 and 749 cm⁻¹ are assigned to the ν₃ (VO₃) antisymmetric stretching vibrations; those at 814 cm⁻¹ to the ν₃ (VOV) antisymmetric vibrations; that at 508 cm⁻¹ to the ν₁ (VOV) symmetric stretching vibration and those at 442 and 476 cm⁻¹ and 347 and 308 cm⁻¹ to the ν₄ (VO₃) and ν₂ (VO₃) bending vibrations, respectively. The spectra of vésigniéite and volborthite are similar, especially in the region of skeletal vibrations, even though their crystal structures differ. Copyright © 2011 John Wiley & Sons, Ltd.     

High‐pressure studies of the micro‐Raman spectra of iron cyanide complexes: Prussian blue (Fe4[Fe(CN)6]3), potassium ferricyanide (K3[Fe(CN)6]), and sodium nitroprusside (Na2[Fe(CN)5(NO)]·2H2O)

The pressure dependences of the peaks observed in the micro‐Raman spectra of Prussian blue (Fe₄[Fe(CN)₆]₃), potassium ferricyanide (K₃[Fe(CN)₆]), and sodium nitroprusside (Na₂[Fe(CN)₅(NO)]·2H₂O) have been measured up to 5.0 GPa. The vibrational modes of Prussian blue appearing at 201 and 365 cm⁻¹ show negative dν/dP values and Grüneisen parameters and are assigned to the transverse bending modes of the Fe C N Fe linkage which can contribute to a negative thermal expansion behavior. A phase transition occurring between 2.0 and 2.8 GPa in potassium ferricyanide is shown by changes in the spectral region 150–700 cm⁻¹. In the spectra of the nitroprusside ion, there are strong interactions between the FeN stretching mode and the FeNO bending and the axial CN stretching modes. The pressure dependence of the NO stretching vibration is positive, 5.6 cm⁻¹ GPa⁻¹, in contrast to the negative behavior in the iron(II)‐meso‐tetraphenyl porphyrinate complex. Copyright © 2011 John Wiley & Sons, Ltd.     

Hopping Transport and Stochastic Dynamics of Electrons in Plasma Layers

We investigate the stochastic dynamics and the hopping transfer of electrons embedded into two‐dimensional atomic layers. First we formulate the quantum statistics of general atom ‐ electron systems based on the tight‐binding approximation and express ‐ following linear response transport theory ‐ the quantum‐mechanical time correlation functions and the conductivity by means of equilibrium time correlation functions. Within the relaxation time approach an expression for the effective collision frequency is derived in Born approximation, which takes into account quantum effects and dynamic effects of the atom motion through the dynamic structure factor of the lattice and the quantum dynamics of the electrons. In the last part we derive Pauli equations for the stochastic electron dynamics including nonlinear excitations of the atomic subsystem. We carry out Monte Carlo simulations and show that mean square displacements of electrons and transport properties are in a moderate to high temperature regime strongly influenced by by soliton‐type excitations and demonstrate the existence of percolation effects (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dust Self‐Organized Structures II. Solutions of Master Equations for Small Diffusion

Master equations for spherical dust structures are solved numerically using the asymptotic solutions at the center of the structures for the case of absence of external ionization and small diffusions. The structures are determined by a single parameter, the external plasma flux at the surface of the structure. The equilibrium states that are possible in a limited range of this parameter are investigated numerically. It is demonstrated that in the range of existence of equilibria the structures are changing their shapes and type of distributions inside the structures. For large external fluxes the ion and dust distributions can have peaks inside the structures while for low external fluxes the dust distribution has a single maximum at the structure center. The lower is the external flux supporting the structure the larger is its size. An increase of the external flux decreases the accumulation of dust and ions at the center. The total number of dust confined by the structure is larger for larger size structures. Estimates of dust crystallization inside structures are given. The role of diffusion is calculated by perturbations and is shown to be small in all structure regions except the structure edges. In the perturbation theory we use the exact expressions of the diffusion coefficients calculated previously numerically. The regions with dust density peaks inside the structures have been calculated with two order of magnitude larger precision that allows to resolve the structure parameter dependencies inside the peaks. It is shown that although in peaks the gradients of all parameters are increased the diffusion flux is still small and that the continuity and hydrodynamic approach are applicable within an accuracy about several %‐s (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Pulse radiolysis studies of 2‐ and 3‐hydroxybenzyl alcohols: inhibition of dehydration of ·OH‐(hydroxybenzyl alcohols) adducts by H2PO4− ions

Reactions of ·OH/O ^.? radicals and H‐atoms as well as specific oxidants such as Cl₂^.? and N₃· radicals have been studied with 2‐ and 3‐hydroxybenzyl alcohols (2‐ and 3‐HBA) at various pH using pulse radiolysis technique. At pH 6.8, ·OH radicals were found to react quite fast with both the HBAs (k = 7.8 × 10⁹ dm³ mol^?1 s^?1 with 2‐HBA and 2 × 10⁹ dm³ mol^?1 s^?1 with 3‐HBA) mainly by adduct formation and to a minor extent by H‐abstraction from ? CH₂OH groups. ·OH‐(HBA) adduct were found to undergo decay to give phenoxyl type radicals in a pH dependent way and it was also very much dependent on buffer‐ion concentrations. It was seen that ·OH‐(2‐HBA) and ·OH‐(3‐HBA) adducts react with HPO₄^2? ions (k = 2.1 × 10⁷ and 2.8 × 10⁷ dm³ mol^?1 s^?1 at pH 6.8, respectively) giving the phenoxyl type radicals of HBAs. At the same time, this reaction is very much hindered in the presence of H₂PO ions indicating the role of phosphate ion concentration in determining the reaction pathway of ·OH adduct decay to final stable product. In the acidic region adducts were found to react with H⁺ ions. At pH 1, reaction of ·OH radicals with HBAs gave exclusively phenoxyl type radicals. Proportion of the reducing radicals formed by H‐abstraction pathway in ·OH/O ^.? reactions with HBAs was determined following electron transfer to methyl viologen. H‐atom abstraction is the major pathway in O ^.? reaction with HBAs compared to ·OH radical reaction. H‐atom reaction with 2‐ and 3‐HBA gave transient species which were found to transfer electron to methyl viologen quantitatively. Copyright © 2010 John Wiley & Sons, Ltd.     

基于改善空间关联性的混沌控制

基于混沌信号的统计特性，提出了一种通过改善混沌信号的空间关联性实现混沌控制的方法.以Hénon离散混沌系统和四阶Chua's电路超混沌连续系统为例进行了数值研究，验证了这种控制方法的有效性.结果表明， 通过改善混沌信号之间的空间关联性， 混沌系统能以较快的速度收敛到它的平衡点或多种周期轨道. 关键词： 混沌控制 空间关联性 Hénon系统 四阶Chua's电路     

Unusually Large Lattice Mismatch‐Induced Optical Behaviors of Au@Cu–Cu2O Core–Shell Nanocrystals with Noncentrally Located Cores

To extend the optical property characterization of metal–Cu₂O polyhedra, 50 nm Au@Cu cubic cores are used to fabricate Au@Cu–Cu₂O core–shell cubes, octahedra, and rhombic dodecahedra with tunable sizes. Despite the unusually large lattice mismatch of 15.1% between Cu and Cu₂O, fine adjustment in the volumes of reagents introduced allows the formation of these heterostructures. To relieve the lattice strain, the metal cores are essentially never found to locate at the particle center, and slight lattice spacing shifts are recorded. Although efforts are made to reduce the heterostructure sizes, the Cu₂O shells are generally too thick to reveal surface plasmon resonance (SPR) absorption band from the metal cores. Only the Au@Cu–Cu₂O cubes with many cores located near the particle corners show observable SPR band red‐shift, but UV–vis spectra of all particle shapes are still dominated by Cu₂O absorption and light scattering bands. Au@Cu–Cu₂O cubes consistently show the most red‐shifted absorption bands than those of octahedra resulting from the optical facet effects.